Use of Maleimide Salts to Control Phytopathogenic Fungi

ABSTRACT

The present invention relates to the use of new and known maleimide salts for controlling phytopathogenic fungi, and also to methods for controlling phytopathogenic fungi in crop protection, in the household and hygiene sectors and in materials protection, and also to crop protection compositions comprising these maleimide salts.

The present invention relates to the use of new and known maleimidesalts for controlling phytopathogenic fungi, and also to methods forcontrolling phytopathogenic fungi in crop protection, in the householdand hygiene sectors and in materials protection, and also to cropprotection compositions comprising these maleimide salts.

Maleimide salts as such are already known (cf. Chem. Ber. 1967, 100,1559-1570). Also known are nickel complexes of maleimide dithiolate (cf.Inorg. Chem. 2005, 44, 3380-3382). It was, however, unknown to date thatthese maleimide salts possess a biological activity and are suitable forcontrolling phytopathogenic fungi in crop protection.

In view of the continually increasing environmental and economicrequirements made on modern fungicides, in terms, for example, ofactivity spectrum, toxicity, selectivity, application rate, residueformation and ease of preparation, and in view, furthermore, of thepossibility of problems occurring with resistances, for example, anever-present object is to develop new fungicides which at least in somerespects go further to fulfilling the stated requirements.

It has now been found that maleimide salts of the general formula (I)

in which

-   (a) Y¹ is the group of the formula (II)

-   -   Y² is the group of the formula (III)

-   -   m is 1, n is the ionic charge of X, and    -   X is an anion selected from Cl⁻ or Br⁻,        or

-   (b) Y¹ is the group of the formula (II)

-   -   Y² is —S⁻,    -   and m is 0,        or

-   (c) Y¹ is —S⁻,    -   Y² is —S⁻,    -   m is 1, n is the ionic charge of X, and    -   X is a cation selected from H⁺, Ag⁺, Co²⁺, Cu²⁺, Fe²⁺, Mn²⁺,        Ni²⁺, Pd²⁺, Zn²⁺,        and

-   R¹ is hydrogen, or is C₁-C₈-alkyl optionally substituted one or more    times by identical or different halogen, —OR¹⁰ and/or —COR¹¹    substituents, C₃-C₇-cycloalkyl or C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each    of which is optionally substituted one or more times by identical or    different halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl substituents, or    aryl, aryl-(C₁-C₄-alkyl) or arylsulphonylamino, each of which is    optionally substituted one or more times by identical or different    halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR¹¹ or sulphonylamino    substituents in the aryl moiety,

-   R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ independently of one another are    hydrogen, C₁-C₆-alkyl, or phenyl or benzyl each of which is    optionally substituted one or more times by identical or different    halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio substituents,

-   R¹⁰ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which is    optionally substituted one or more times by halogen, C₁-C₄-alkyl or    C₁-C₄-haloalkyl substituents,

-   R¹¹ is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy,    can be used to very good effect for controlling phytopathogenic    fungi.

Maleimide salts of the formula (I) according to the invention areexceptionally suitable for controlling harmful phytopathogenic fungi.The aforementioned compounds of the invention display in particular afungicidal activity and can be used in crop protection, in the householdand hygiene sectors and in materials protection.

The maleimide salts which can be used in accordance with the inventionhave a general definition provided by the formula (I). With preferenceit is possible to use maleimide salts of the formula (I) in which theradicals have the definitions below.

-   R¹ preferably is hydrogen, or is C₁-C₆-alkyl optionally substituted    one or more times by identical or different fluorine, chlorine,    bromine, —OR¹⁰ and/or —COR¹¹ substituents, or is C₃-C₇-cycloalkyl or    C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which is optionally    substituted one or more times by identical or different chlorine,    methyl or trifluoromethyl substituents, or is phenyl,    phenyl-(C₁-C₄-alkyl) or phenylsulphonylamino, each of which is    optionally substituted one or more times by identical or different    fluorine, chlorine, bromine, methyl, trifluoromethyl, —COR¹¹ and/or    sulphonylamino substituents.-   R¹ more preferably is hydrogen, or is C₁-C₅-alkyl optionally    substituted one or more times by identical or different fluorine,    chlorine, hydroxyl, methoxy, ethoxy, methylcarbonyloxy and/or    carboxyl substituents, or is cyclopropylmethyl or C₃-C₇-cycloalkyl    optionally substituted one or more times by identical or different    chlorine, methyl or trifluoromethyl substituents, or is phenyl,    benzyl, 1-phenethyl, 2-phenethyl or 2-methyl-2-phenethyl, each of    which is optionally substituted one to three times by identical or    different fluorine, chlorine, bromine, methyl, trifluoromethyl,    —COR¹¹ and/or sulphonylamino substituents.-   R¹ very preferably is hydrogen, methyl, ethyl, n-propyl, isopropyl,    2,2-difluoroethyl or 2,2,2-trifluoroethyl, or is cyclopropyl or    cyclohexyl, each of which is optionally substituted by chlorine,    methyl or trifluoromethyl substituents.-   R¹ and R¹⁰ with more particular preference are simultaneously    methyl.-   R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ independently of one another    preferably are hydrogen, C₁-C₄-alkyl, phenyl or benzyl.-   R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and R⁹ independently of one another more    preferably are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-,    iso-, sec- or tert-butyl.

If X is an anion, X preferably is chlorine.

If X is a cation, X preferably is H⁺, Ag⁺, Fe²⁺, Mn²⁺ or Zn²⁺.

If X is a cation, X more preferably is Ag⁺, Mn²⁺ or Zn²⁺.

-   R¹⁰ preferably is hydrogen, methyl, ethyl, methylcarbonyl or    ethylcarbonyl, or is phenyl which is optionally substituted one or    more times by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl    or trifluoromethyl substituents.-   R¹⁰ more preferably is hydrogen, methyl or methylcarbonyl or is    phenyl.-   R¹¹ preferably is hydroxyl, methyl, ethyl, methoxy or ethoxy.-   R¹¹ more preferably is hydroxyl or methoxy.

Specifically, reference is made to the compounds stated in thePreparation Examples.

With preference it is possible to use more particularly the compounds ofthe formula (Ia)

in which m is 1, n is the ionic charge of X,

-   X is an anion selected from Cl⁻ or Br⁻, and-   R¹ to R⁹ have the above-indicated general, preferred, more    preferred, etc. definitions.

New in this context are the maleimide salts of the formula (IV)

in which

-   R^(1a) is hydrogen, or is C₁-C₈-alkyl optionally substituted one or    more times by identical or different halogen, —OR^(10a) and/or    —COR^(11a) substituents, C₃-C₇-cycloalkyl or    C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which is optionally    substituted one or more times by identical or different halogen,    C₁-C₄-alkyl or C₁-C₄-haloalkyl substituents, or aryl,    aryl-(C₁-C₄-alkyl) or arylsulphonylamino, each of which is    optionally substituted one or more times by identical or different    halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR^(11a) or sulphonylamino    substituents in the aryl moiety,-   R^(2a), R^(3a), R^(4a), R^(5a), R^(6a), R^(7a), R^(8a) and R^(9a)    independently of one another are hydrogen, C₁-C₆-alkyl, or phenyl or    benzyl each of which is optionally substituted one or more times by    identical or different halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or    C₁-C₄-alkylthio substituents,    -   where R^(2a), R^(3a), R^(4a) and R^(5a) are not all        simultaneously hydrogen if R^(1a) is hydrogen, methyl,        hydroxymethyl, methylcarbonyloxymethyl, chloromethyl, benzyl,        phenyl or methoxymethyl and X^(a) is chlorine,-   R^(10a) is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which    is optionally substituted one or more times by halogen, C₁-C₄-alkyl    or C₁-C₄-haloalkyl substituents,-   R^(11a) is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy,-   m is 1, n is the ionic charge of X^(a), and-   X^(a) is an anion selected from Cl⁻ or Br⁻.

R^(1a) to R^(11a) and X^(a) here, moreover, have the preferred, morepreferred, very preferred, etc., definitions stated above for thecorresponding radicals R¹ to R¹¹ and X (anion), the stated compoundsbeing furthermore excluded.

In another embodiment of this invention, it is possible with preferenceto use the compounds of the formula (Ib)

in which R¹ to R⁵ have the above-indicated general, preferred, morepreferred, etc., definitions.

New in this context are the maleimide salts of the formula (V)

in which

-   R^(1b) is hydrogen, or is C₁-C₈-alkyl optionally substituted one or    more times by identical or different halogen, —OR^(10b) and/or    —COR^(11b) substituents, C₃-C₇-cycloalkyl or    C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which is optionally    substituted one or more times by identical or different halogen,    C₁-C₄-alkyl or C₁-C₄-haloalkyl substituents, or aryl,    aryl-(C₁-C₄-alkyl) or arylsulphonylamino, each of which is    optionally substituted one or more times by identical or different    halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR^(11b) or sulphonylamino    substituents in the aryl moiety,-   R^(2b), R^(3b), R^(4b), and R^(5b) independently of one another are    hydrogen, C₁-C₆-alkyl, or phenyl or benzyl each of which is    optionally substituted one or more times by identical or different    halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio substituents,    -   where R^(2b), R^(3b), R^(4b) and R^(5b) are not all        simultaneously hydrogen if R^(1b) is hydrogen, methyl,        hydroxymethyl, methylcarbonyloxymethyl, chloromethyl, benzyl,        phenyl or methoxymethyl,-   R^(10b) is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which    is optionally substituted one or more times by halogen, C₁-C₄-alkyl    or C₁-C₄-haloalkyl substituents,-   R^(11b) is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy.

R^(1b) to R^(5b), R^(10b) and R^(11b) here, moreover, have thepreferred, more preferred, very preferred, etc., definitions statedabove for the corresponding radicals R¹ to R⁵, R¹⁰ and R¹¹, the statedcompounds being furthermore excluded.

In another embodiment of this invention it is possible with preferenceto use the compounds of the formula (Ic)

in which m is 1, n is the ionic charge of X, and

-   X is a cation selected from H⁺, Ag⁺, Co²⁺, Cu²⁺, Fe²⁺, Mn²⁺, Ni²⁺,    Pd²⁺ and Zn²⁺, and-   R¹ has the above-indicated general, preferred, more preferred, etc.,    definitions.

If X is H⁺ in compounds of the formula (I) or (Ic), the mercapto groupSH is obtained in each case.

New in this context are the maleimide salts of the formula (VI)

in which

-   R^(1c) is hydrogen, or is C₁-C₈-alkyl optionally substituted one or    more times by identical or different halogen, —OR^(10c) and/or    —COR^(11c) substituents, C₃-C₇-cycloalkyl or    C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which is optionally    substituted one or more times by identical or different halogen,    C₁-C₄-alkyl or C₁-C₄-haloalkyl substituents, or aryl,    aryl-(C₁-C₄-alkyl) or arylsulphonylamino, each of which is    optionally substituted one or more times by identical or different    halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR^(11c) or sulphonylamino    substituents in the aryl moiety,-   R^(10c) is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which    is optionally substituted one or more times by halogen, C₁-C₄-alkyl    or C₁-C₄-haloalkyl substituents,-   R^(11c) is hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy,-   m is 1, n is the ionic charge of X^(c), and-   X^(c) is a cation selected from Ag⁺, Co²⁺, Cu²⁺, Fe²⁺, Mn²⁺, Ni²⁺,    Pd²⁺ and Zn²⁺, where X^(c) is not Ag⁺ if R^(1c) is hydrogen, methyl,    hydroxymethyl, methylcarbonyloxymethyl, chloromethyl, benzyl, phenyl    or methoxymethyl.

R^(1c), R^(10c), R^(11c) and X^(c) and n here, moreover, have thepreferred, more preferred, very preferred, etc., definitions statedabove for the corresponding radicals R¹, R¹⁰, R¹¹ and X (cation), thestated compounds being furthermore excluded.

In the maleimide salts of the formula (I) and also in the formulae (Ia),(Ib), (IV) and (V), the urea substituents may occur in two differentisomeric forms, which may be particularly pronounced in the case ofdifferent substituents R² to R⁹:

For the sake of simplicity, only one possible form is shown in eachcase.

All of the maleimide salts of the formula (I) that can be used inaccordance with the invention may optionally be present in polymericform, especially the maleimide salts of the formula (Ic) in dimercaptoform.

The maleimide salts of the formula (I) that can be used in accordancewith the invention can be prepared in a known way (cf. Chem. Ber. 1967,100, 1559-1570).

For example, in a first stage, maleimides of the formula (VII) arereacted with thioureas of the formulae (VIII) and (IX) in non-aqueoussolvents to give the maleimide salts of the formula (I). Mild alkalinehydrolysis yields saltlike compounds of the formula (II). Maleimidesalts of the formula (III) can be obtained alternatively byprecipitation with metal salts in ammoniacal solution from the compoundsof the formulae (II) or (III).

The present invention relates, furthermore, to a crop protectioncomposition for controlling unwanted fungi, comprising at least one ofthe maleimide salts of the formula (I). The compositions in question arepreferably fungicidal compositions which comprise agriculturally usefulauxiliaries, solvents, carriers, surface-active substances or extenders.

The invention relates, moreover, to a method for controlling unwantedmicroorganisms, characterized in that, in accordance with the invention,maleimide salts of the formula (I) are delivered to the phytopathogenicfungi and/or their habitat.

In accordance with the invention, “carrier” denotes a natural orsynthetic, organic or inorganic substance with which the activeingredients are joined or mixed for greater ease of application,including for application to plants or plant parts or seed. The carrier,which may be solid or liquid, is generally inert and ought to besuitable for use in agriculture.

Suitable solid or liquid carriers are: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and natural orsynthetic silicates, resins, waxes, solid fertilizers, water, alcohols,especially butanol, organic solvents, mineral and vegetable oils andderivatives of these. Mixtures of such carriers may also be used.Suitable solid carriers for granules are: for example crushed andfractionated natural minerals, such as calcite, marble, pumice,sepiolite, dolomite, and also synthetic granules of inorganic andorganic meals and also granules of organic material, such as sawdust,coconut shells, maize cobs and tobacco stalks.

Suitable liquefied gaseous extenders or carriers are liquids which aregaseous at ambient temperature and under atmospheric pressure, forexample aerosol propellants, such as halohydrocarbons, and also butane,propane, nitrogen and carbon dioxide.

Tackifiers, such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or lattices, such as gumarabic, polyvinyl alcohol, polyvinyl acetate, or else naturalphospholipids, such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

If the extender used is water, it is also possible, for example, to useorganic solvents as auxiliary solvents. Suitable liquid solvents areessentially: aromatic compounds, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatic compounds or chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ordichloromethane, aliphatic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, mineral and vegetableoils, alcohols, such as butanol or glycol, and also ethers and estersthereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutylketone or cyclohexanone, strongly polar solvents, such asdimethylformamide and dimethyl sulphoxide, and also water.

The compositions according to the invention may comprise additionalfurther components, such as, for example, surface-active substances.Suitable surface-active substances are emulsifiers and/or foam-formers,dispersants or wetting agents having ionic or nonionic properties, ormixtures of these surface-active substances. Examples of these are saltsof polyacrylic acid, salts of lignosulphonic acid, salts ofphenolsulphonic acid or naphthalenesulphonic acid, polycondensates ofethylene oxide with fatty alcohols or with fatty acids or with fattyamines, substituted phenols (preferably alkylphenols or arylphenols),salts of sulphosuccinic esters, taurine derivatives (preferably alkyltaurates), phosphoric esters of polyethoxylated alcohols or phenols,fatty acid esters of polyols, and derivatives of the compoundscontaining sulphates, sulphonates and phosphates, for example, alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,protein hydrolysates, ligno-sulphite waste liquors and methylcellulose.The presence of a surface-active substance is required if one of theactive compounds and/or one of the inert carriers is insoluble in waterand when the application takes place in water. The proportion ofsurface-active substances is between 5 and 40 percent by weight of thecomposition according to the invention.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide, Prussian blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients, such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

If appropriate, other additional components may also be present, forexample protective colloids, binders, adhesives, thickeners, thixotropicsubstances, penetrants, stabilizers, sequestering agents,complex-formers. In general, the active compounds can be combined withany solid or liquid additive customarily used for formulation purposes.

In general, the formulations contain between 0.05 and 99% by weight,0.01 and 98% by weight, preferably between 0.1 and 95% by weight,especially preferably between 0.5 and 90% by weight of active compound,very especially preferably between 10 and 70 percent by weight.

The active compounds or compositions according to the invention can beused as such or, depending on their respective physical and/or chemicalproperties, in the form of their formulations or the use forms preparedtherefrom, such as aerosols, capsule suspensions, cold-foggingconcentrates, warm-fogging concentrates, encapsulated granules, finegranules, flowable concentrates for the treatment of seed, ready-to-usesolutions, dustable powders, emulsifiable concentrates, oil-in-wateremulsions, water-in-oil emulsions, macrogranules, microgranules,oil-dispersible powders, oil-miscible flowable concentrates,oil-miscible liquids, foams, pastes, pesticide-coated seed, suspensionconcentrates, suspoemulsion concentrates, soluble concentrates,suspensions, wettable powders, soluble powders, dusts and granules,water-soluble granules or tablets, water-soluble powders for thetreatment of seed, wettable powders, natural products and syntheticsubstances impregnated with active compound, and alsomicroencapsulations in polymeric substances and in coating materials forseed, and also ULV cold-fogging and warm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one customaryextender, solvent or diluent, emulsifier, dispersant and/or binder orfixing agent, wetting agent, water repellent, if appropriate siccativesand UV stabilizers and, if appropriate, dyes and pigments, defoamers,preservatives, secondary thickeners, adhesives, gibberellins and alsofurther processing auxiliaries.

The compositions according to the invention do not only compriseready-to-use formulations which can be applied with a suitable apparatusto the plant or the seed, but also commercial concentrates which have tobe diluted with water prior to use.

The active compounds according to the invention, per se or in their(commercially available) formulations and in the use forms prepared fromthese formulations, may be present in a mixture with other (known)active compounds such as insecticides, attractants, sterilants,bactericides, acaricides, nematicides, fungicides, growth regulators,herbicides, fertilizers, safeners or semiochemicals.

The treatment according to the invention of the plants and plant partswith the active compounds or compositions is carried out directly or byaction on their surroundings, habitat or storage space using customarytreatment methods, for example by dipping, spraying, atomizing,irrigating, evaporating, dusting, fogging, broadcasting, foaming,painting, spreading-on, drenching, drip irrigating and, in the case ofpropagation material, in particular in the case of seeds, furthermore bydry seed treatment, by wet seed treatment, by slurry treatment, byincrusting, by coating with one or more coats, etc. It is furthermorepossible to apply the active compounds by the ultra-low-volume method,or to inject the active compound preparation, or the active compounditself, into the soil.

The invention furthermore comprises a method for the treatment of seed.

The invention furthermore relates to seed which has been treated inaccordance with one of the methods described in the previous paragraph.The seeds according to the invention are used in methods for theprotection of seed from undesirable fungi. Here, a seed treated with atleast one active compound according to the invention is used.

The active compounds or compositions according to the invention are alsosuitable for treating seed. A large part of the damage to crop plantscaused by harmful organisms is triggered by the infection of the seedduring storage or after sowing as well as during and after germinationof the plant. This phase is particularly critical since the roots andshoots of the growing plant are particularly sensitive, and even justsmall damage may result in the death of the plant. Accordingly, there isgreat interest in protecting the seed and the germinating plant by usingappropriate compositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of continuousimprovements. However, the treatment of seed entails a series ofproblems which cannot always be solved in a satisfactory manner. Thus,it is desirable to develop methods for protecting the seed and thegerminating plant which dispense with the additional application of cropprotection compositions after sowing or after the emergence of theplants or which at least considerably reduce additional application. Itis furthermore desirable to optimize the amount of active compoundemployed in such a way as to provide maximum protection for the seed andthe germinating plant from attack by phytopathogenic fungi, but withoutdamaging the plant itself by the active compound employed. Inparticular, methods for the treatment of seed should also take intoconsideration the intrinsic fungicidal properties of transgenic plantsin order to achieve optimum protection of the seed and the germinatingplant with a minimum of crop protection compositions being employed.

Accordingly, the present invention also relates to a method forprotecting seed and germinating plants against attack by phytopathogenicfungi by treating the seed with a composition according to theinvention. The invention also relates to the use of the compositionsaccording to the invention for treating seed for protecting the seed andthe germinating plant against phytopathogenic fungi. Furthermore, theinvention relates to seed treated with a composition according to theinvention for protection against phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis carried out primarily by treating the soil and the above-ground partsof plants with crop protection compositions. Owing to the concernsregarding a possible impact of the crop protection compositions on theenvironment and the health of humans and animals, there are efforts toreduce the amount of active compounds applied.

One of the advantages of the present invention is that, because of theparticular systemic properties of the active compounds or compositionsaccording to the invention, treatment of the seed with these activecompounds or compositions not only protects the seed itself, but alsothe resulting plants after emergence, from phytopathogenic fungi. Inthis manner, the immediate treatment of the crop at the time of sowingor shortly thereafter can be dispensed with.

It is also considered to be advantageous that the active compounds orcompositions according to the invention can be used in particular alsofor transgenic seed where the plant growing from this seed is capable ofexpressing a protein which acts against pests. By treating such seedwith the active compounds or compositions according to the invention,even by the expression of the, for example, insecticidal protein,certain pests may be controlled. Surprisingly, a further synergisticeffect may be observed here, which additionally increases theeffectiveness of the protection against attack by pests.

The compositions according to the invention are suitable for protectingseed of any plant variety employed in agriculture, in the greenhouse, inforests or in horticulture and viticulture. In particular, this takesthe form of seed of cereals (such as wheat, barley, rye, triticale,sorghum/millet and oats), maize, cotton, soya beans, rice, potatoes,sunflower, bean, coffee, beet (for example sugar beet and fodder beet),peanut, oilseed rape, poppy, olive, coconut, cacao, sugar cane, tobacco,vegetables (such as tomato, cucumbers, onions and lettuce), turf andornamentals (see also hereinbelow). Of particular importance is thetreatment of the seed of cereals (such as wheat, barley, rye, triticaleand oats), maize and rice.

As also described hereinbelow, the treatment of transgenic seed with theactive compounds or compositions according to the invention is ofparticular importance. This refers to the seed of plants containing atleast one heterologous gene which allows the expression of a polypeptideor protein having insecticidal properties. The heterologous gene intransgenic seed can originate, for example, from microorganisms of thespecies Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. Preferably, this heterologous geneis from Bacillus sp., the gene product having activity against theEuropean corn borer and/or the Western corn rootworm. Particularlypreferably, the heterologous gene originates from Bacillusthuringiensis.

In the context of the present invention, the composition according tothe invention is applied on its own or in a suitable formulation to theseed. Preferably, the seed is treated in a state in which it issufficiently stable so that the treatment does not cause any damage. Ingeneral, treatment of the seed may take place at any point in timebetween harvesting and sowing. Usually, the seed used has been separatedfrom the plant and freed from cobs, shells, stalks, coats, hairs or theflesh of the fruits. Thus, it is possible to use, for example, seedwhich has been harvested, cleaned and dried to a moisture content ofless than 15% by weight. Alternatively, it is also possible to use seedwhich, after drying, has been treated, for example, with water and thendried again.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active compounds which may have phytotoxic effects at certainapplication rates.

The compositions according to the invention can be applied directly,that is to say without comprising further components and without havingbeen diluted. In general, it is preferable to apply the compositions tothe seed in the form of a suitable formulation. Suitable formulationsand methods for the treatment of seed are known to the person skilled inthe art and are described, for example, in the following documents: U.S.Pat. No. 4,272,417 A, U.S. Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430A, U.S. Pat. No. 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO2002/028186 A2.

The active compounds which can be used according to the invention can beconverted into the customary seed-dressing product formulations such assolutions, emulsions, suspensions, powders, foams, slurries and othercoating compositions for seed, and ULV formulations.

These formulations are prepared in the known manner by mixing the activecompounds with customary additives such as, for example, customaryextenders and also solvents or diluents, colorants, wetting agents,dispersants, emulsifiers, defoamer, preservatives, secondary thickeners,adhesives, gibberellins, and also water.

Colorants which may be present in the seed-dressing product formulationswhich can be used according to the invention are all colorants which arecustomary for such purposes. Both pigments, which are sparingly solublein water, and dyes, which are soluble in water, may be used. Examples ofcolorants which may be mentioned are those known by the names RhodaminB, C.I. Pigment Red 112 and C.I. Solvent Red 1.

Wetting agents which may be present in the seed-dressing productformulations which can be used according to the invention are allsubstances which are conventionally used for the formulation ofagrochemical active compounds and for promoting wetting.Alkylnaphthalenesulphonates, such as diisopropyl- ordiisobutylnaphthalenesulphonates, can preferably be used.

Suitable dispersants and/or emulsifiers which may be present in theseed-dressing product formulations which can be used in accordance withthe invention are all non-ionic, anionic and cationic dispersants whichare conventionally used for the formulation of agrochemical activecompounds. Non-ionic or anionic dispersants or mixtures of non-ionic oranionic dispersants can preferably be used. Suitable non-ionicdispersants which may be mentioned are, in particular, ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ethers, and their phosphated or sulfatedderivatives. Suitable anionic dispersants are, in particular,lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Defoamers which may be present in the seed-dressing product formulationswhich can be used according to the invention are all foam-suppressingsubstances conventionally used for the formulation of agrochemicalactive compounds. Silicone defoamers and magnesium stearate canpreferably be used.

Preservatives which may be present in the seed-dressing productformulations which can be used according to the invention are allsubstances which can be employed in agrochemical compositions for suchpurposes. Examples which may be mentioned are dichlorophene and benzylalcohol hemiformal.

Secondary thickeners which may be present in the seed-dressing productformulations which can be used according to the invention are allsubstances which can be employed in agrochemical compositions for suchpurposes. Cellulose derivatives, acrylic acid derivatives, xanthan,modified clays and highly disperse silica are preferably suitable.

Adhesives which may be present in the seed-dressing product formulationswhich can be used according to the invention are all customary binderswhich can be employed in seed-dressing products. Polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned bypreference.

Gibberellins which may be present in the seed-dressing productformulations which can be used according to the invention are preferablythe gibberellins A1, A3 (=gibberelic acid), A4 and A7, with gibberelicacid being particularly preferably used. The gibberellins are known (cf.R. Wegler “Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel”[Chemistry of Plant Protectants and Pesticides], Vol. 2, SpringerVerlag, 1970, pp. 401-412).

The seed-dressing product formulations which can be used in accordancewith the invention can be employed either directly or after previousdilution with water for the treatment of a wide range of seeds,including the seed of transgenic plants. In this context, additionalsynergistic effects may also occur as a consequence of the interactionwith the substances formed by expression.

Suitable apparatuses which can be employed for treating seed with theseed-dressing product formulations which can be used in accordance withthe invention, or with the preparations prepared therefrom by additionof water, are all mixing apparatuses which can usually be employed fordressing seed. Specifically, a seed-dressing procedure is followed inwhich the seed is placed in a mixer, the amount of seed-dressing productformulation desired in each case is added, either as such or afterpreviously diluting it with water, and the contents of the mixer aremixed until the formulation has been distributed uniformly on the seed.If appropriate, this is followed by a drying process.

The active compounds or compositions according to the invention have apotent fungicidal activity and can be employed for controlling unwantedfungi in crop protection and in the protection of materials.

The maleimide salts according to the invention can be used in cropprotection for controlling Plasmodiophoromycetes, Oomycetes,Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes andDeuteromycetes.

The fungicidal compositions according to the invention can be employedcuratively or protectively for controlling phytopathogenic fungi. Theinvention therefore also relates to curative and protective methods ofcontrolling phytopathogenic fungi by using the active compounds orcompositions according to the invention, which are applied to the seed,the plant or plant parts, the fruits or the soil in which the plantsgrow.

The compositions according to the invention for controllingphytopathogenic fungi in plant protection comprise an effective, butnonphytotoxic, amount of the active compounds according to theinvention. “Effective, but nonphytotoxic amount” means such an amount ofthe composition according to the invention which suffices forsufficiently controlling or fully eradicating the fungal disease of theplant while simultaneously not entailing substantial phytotoxicitysymptoms. In general, this application rate can vary within asubstantial range. It depends on a plurality of factors, for example onthe fungus to be controlled, the plant, the climatic conditions and theconstituents of the compositions according to the invention.

The good plant tolerance of the active compounds at the concentrationsrequired for controlling plant diseases permits the treatment of aerialplant parts, of vegetative propagation material and of seed, and of thesoil.

All plants and plant parts can be treated in accordance with theinvention. In the present context, plants are understood as meaning allplants and plant populations, such as desired and undesired wild plantsor crop plants (including naturally occurring crop plants). Crop plantscan be plants which can be obtained by traditional breeding andoptimization methods or by biotechnological and recombinant methods, orcombinations of these methods, including the transgenic plants andincluding the plant varieties capable or not of being protected by PlantBreeders' Rights. Plant parts are understood as meaning all aerial andsubterranean parts and organs of the plants, such as shoot, leaf, flowerand root, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruiting bodies, fruits and seeds, and also roots,tubers and rhizomes. The plant parts also include the harvested materialand vegetative and generative propagation material, for examplecuttings, tubers, rhizomes, slips and seeds.

The active compounds according to the invention are suitable for theprotection of plants and plant organs, for increasing the yields, forimproving the quality of the harvested crop, while being well toleratedby plants, having favourable toxicity to warm-blooded species and beingenvironmentally friendly. They can preferably be employed as cropprotection compositions. They are active against normally sensitive andresistant species and against all or individual developmental stages.

Plants which can be treated in accordance with the invention and whichmay be mentioned are the following: cotton, flax, grapevine, fruit,vegetables, such as Rosaceae sp. (for example pome fruits such as applesand pears, but also stone fruits such as apricots, cherries, almonds andpeaches, and soft fruits such as strawberries), Ribesioidae sp.,Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp.,Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceaesp. (for example banana plants and banana plantations), Rubiaceae sp.(for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (forexample lemons, oranges and grapefruit); Solanaceae sp. (for exampletomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce),Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp.(for example cucumbers), Alliaceae sp. (for example leeks, onions),Papilionaceae sp. (for example peas); major crop plants such asGramineae sp. (for example maize, turf, cereals such as wheat, rye,rice, barley, oats, sorghum, millet and triticale), Asteraceae sp. (forexample sunflower), Brassicaceae sp. (for example white cabbage, redcabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi,small radishes, and also oilseed rape, mustard, horseradish and cress),Fabacae sp. (for example beans, peanuts), Papilionaceae sp. (for examplesoya beans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp.(for example sugar beet, fodder beet, Swiss chard, beetroot); usefulplants and ornamental plants in gardens and forests; and in each casegenetically modified types of these plants.

As has already been mentioned above, all plants and their parts may betreated in accordance with the invention. In a preferred embodiment,plant species and plant varieties, and their parts, which grow wild orwhich are obtained by traditional biological breeding methods such ashybridization or protoplast fusion are treated. In a further preferredembodiment, transgenic plants and plant varieties which have beenobtained by recombinant methods, if appropriate in combination withtraditional methods (genetically modified organisms), and their partsare treated. The term “parts” or “parts of plants” or “plant parts” hasbeen explained hereinabove. Plants of the plant varieties which are ineach case commercially available or in use are especially preferablytreated in accordance with the invention. Plant varieties are understoodas meaning plants with novel traits which have been bred both bytraditional breeding, by mutagenesis or by recombinant DNA techniques.They may take the form of varieties, subspecies, biotypes and genotypes.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for exampleantisense technology, cosuppression technology or RNAinterference—RNAi-technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf colour, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which effectsexceed the effects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are suitable for mobilizing the defense system of theplant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, also those substances or combinations of substanceswhich are capable of stimulating the defense system of plants in such away that, when subsequently inoculated with unwanted phytopathogenicfungi, the treated plants display a substantial degree of resistance tothese unwanted phytopathogenic fungi. Thus, the substances according tothe invention can be employed for protecting plants against attack bythe abovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active compounds.

Plants and plant varieties which are preferably to be treated accordingto the invention include all plants which have genetic material whichimparts particularly advantageous, useful traits to these plants(whether obtained by breeding and/or biotechnological means).

Plants and plant varieties which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants have a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant varieties which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, waterlogging,increased soil salinity, increased exposure to minerals, exposure toozone, exposure to strong light, limited availability of nitrogennutrients, limited availability of phosphorus nutrients or shadeavoidance.

Plants and plant varieties which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Enhanced yield in said plants can be the result of, forexample, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigor, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis, or hybrid vigor,which results in generally higher yield, vigor, better health andresistance towards biotic and abiotic stress factors. Such plants aretypically made by crossing an inbred male-sterile parent line (thefemale parent) with another inbred male-fertile parent line (the maleparent). Hybrid seed is typically harvested from the male-sterile plantsand sold to growers. Male-sterile plants can sometimes (e.g. in corn) beproduced by detasseling (i.e. the mechanical removal of the malereproductive organs or male flowers) but, more typically, male sterilityis the result of genetic determinants in the plant genome. In that case,and especially when seed is the desired product to be harvested from thehybrid plants, it is typically useful to ensure that male fertility inthe hybrid plants, which contain the genetic determinants responsiblefor male sterility, is fully restored. This can be accomplished byensuring that the male parents have appropriate fertility restorer geneswhich are capable of restoring the male fertility in hybrid plants thatcontain the genetic determinants responsible for male sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedfor Brassica species. However, genetic determinants for male sterilitycan also be located in the nuclear genome. Male-sterile plants can alsobe obtained by plant biotechnology methods such as genetic engineering.A particularly useful means of obtaining male-sterile plants isdescribed in WO 89/10396 in which, for example, a ribonuclease such as abarnase is selectively expressed in the tapetum cells in the stamens.Fertility can then be restored by expression in the tapetum cells of aribonuclease inhibitor such as barstar.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containing naturallyoccurring mutations of the abovementioned genes.

Other herbicide-resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition. One such efficientdetoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase are described.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyse thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD inhibitors can be transformedwith a gene encoding a naturally occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme of prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Further herbicide-resistant plants are plants that are made tolerant toacetolactate synthase (ALS) inhibitors. Known ALS inhibitors include,for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates, and/or sulphonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides. The production ofsulphonylurea-tolerant plants and imidazolinone-tolerant plants has beendescribed in the international publication WO 1996/033270. Furthersulphonylurea- and imidazolinone-tolerant plants have also beendescribed, for example in WO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

The term “insect-resistant transgenic plant”, as used herein, includesany plant containing at least one transgene comprising a coding sequenceencoding:

1) an insecticidal crystal protein from Bacillus thuringiensis or aninsecticidal portion thereof, such as the insecticidal crystal proteinslisted online at:

http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or insecticidalportions thereof, e.g. proteins of the Cry protein classes Cry1Ab,Cry1Ac, Cry1F, Cry2Ab, Cry3Ae, or Cry3Bb or insecticidal portionsthereof; or

2) a crystal protein from Bacillus thuringiensis or a portion thereofwhich is insecticidal in the presence of a second other crystal proteinfrom Bacillus thuringiensis or a portion thereof, such as the binarytoxin made up of the Cy34 and Cy35 crystal proteins; or3) a hybrid insecticidal protein comprising parts of two differentinsecticidal crystal proteins from Bacillus thuringiensis, such as ahybrid of the proteins of 1) above or a hybrid of the proteins of 2)above, e.g. the Cry1A.105 protein produced by maize event MON98034 (WO2007/027777); or4) a protein of any one of 1) to 3) above wherein some, particularly 1to 10, amino acids have been replaced by another amino acid to obtain ahigher insecticidal activity to a target insect species, and/or toexpand the range of target insect species affected, and/or because ofchanges induced into the encoding DNA during cloning or transformation,such as the Cry3Bb1 protein in maize events MON863 or MON88017, or theCry3A protein in maize event MIR 604;5) an insecticidal secreted protein from Bacillus thuringiensis orBacillus cereus, or an insecticidal portion thereof, such as thevegetative insecticidal proteins (VIP) listed athttp://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html, e.g.proteins from the VIP3Aa protein class; or6) a secreted protein from Bacillus thuringiensis or Bacillus cereuswhich is insecticidal in the presence of a second secreted protein fromBacillus thuringiensis or B. cereus, such as the binary toxin made up ofthe VIP1A and VIP2A proteins; or7) a hybrid insecticidal protein comprising parts from differentsecreted proteins from Bacillus thuringiensis or Bacillus cereus, suchas a hybrid of the proteins in 1) above or a hybrid of the proteins in2) above; or8) a protein of any one of 1) to 3) above wherein some, particularly 1to 10, amino acids have been replaced by another amino acid to obtain ahigher insecticidal activity to a target insect species, and/or toexpand the range of target insect species affected, and/or because ofchanges induced into the encoding DNA during cloning or transformation(while still encoding an insecticidal protein), such as the VIP3Aaprotein in cotton event COT 102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay development of insectresistance to the plants, by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

a. plants which contain a transgene capable of reducing the expressionand/or the activity of the poly(ADP-ribose)polymerase (PARP) gene in theplant cells or plants.b. plants which contain a stress tolerance-enhancing transgene capableof reducing the expression and/or the activity of the PARG-encodinggenes of the plants or plant cells.c. plants which contain a stress tolerance-enhancing transgene codingfor a plant-functional enzyme of the nicotinamide adenine dinucleotidesalvage biosynthesis pathway, including nicotinamidase, nicotinatephosphoribosyltransferase, nicotinic acid mononucleotideadenyltransferase, nicotinamide adenine dinucleotide synthetase ornicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage stability of theharvested material and/or altered properties of specific ingredients ofthe harvested material such as:

1) transgenic plants which synthesize a modified starch, which in itsphysical-chemical characteristics, in particular the amylose content orthe amylose/amylopectin ratio, the degree of branching, the averagechain length, the side chain distribution, the viscosity behavior, thegelling strength, the starch grain size and/or the starch grainmorphology, is changed in comparison with the synthesized starch in wildtype plant cells or plants, so that this modified starch is bettersuited for special applications.2) transgenic plants which synthesize non-starch carbohydrate polymersor which synthesize non-starch carbohydrate polymers with alteredproperties in comparison to wild type plants without geneticmodification. Examples are plants which produce polyfructose, especiallyof the inulin and levan type, plants which produce alpha-1,4-glucans,plants which produce alpha-1,6 branched alpha-1,4-glucans, and plantsproducing alternan.3) transgenic plants which produce hyaluronan.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibrecharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfibre characteristics and include:

a) plants, such as cotton plants, which contain an altered form ofcellulose synthase genes;b) plants, such as cotton plants, which contain an altered form of rsw2or rsw3 homologous nucleic acids;c) plants, such as cotton plants, with an increased expression ofsucrose phosphate synthase;d) plants, such as cotton plants, with an increased expression ofsucrose synthase;e) plants, such as cotton plants, wherein the timing of theplasmodesmatal gating at the basis of the fibre cell is altered, e.g.through downregulation of fibre-selective β-1,3-glucanase;f) plants, such as cotton plants, which have fibres with alteredreactivity, e.g. through the expression of theN-acetylglucosaminetransferase gene, including nodC, and chitin synthasegenes.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as oilseed rape or related Brassica plants,with altered oil profile characteristics. Such plants can be obtained bygenetic transformation or by selection of plants containing a mutationimparting such altered oil characteristics and include:

a) plants, such as oilseed rape plants, which produce oil having a higholeic acid content;b) plants, such as oilseed rape plants, which produce oil having a lowlinolenic acid content;c) plants, such as oilseed rape plants, which produce oil having a lowlevel of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins and are the following which are sold under the tradenames YIELD GARD® (for example maize, cotton, soya beans), KnockOut®(for example maize), BiteGard® (for example maize), BT-Xtra® (forexample maize), StarLink® (for example maize), Bollgard® (cotton),Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example maize),Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plantswhich may be mentioned are maize varieties, cotton varieties and soyabean varieties which are sold under the trade names Roundup Ready®(tolerance to glyphosate, for example maize, cotton, soya beans),Liberty Link® (tolerance to phosphinothricin, for example oilseed rape),IMI® (tolerance to imidazolinone) and SCS (tolerance to sulphonylurea,for example maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, that are listed for example in thedatabases for various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

The active compounds or compositions according to the invention mayfurthermore be employed in the protection of materials for protectingindustrial materials against attack and destruction by undesiredmicroorganisms such as, for example, fungi.

In the present context, industrial materials are understood as meaningnonliving materials which have been prepared for use in industry.Industrial materials which are intended to be protected by activecompounds according to the invention from fungal change or destructioncan be, for example, glues, sizes, paper, wall card and board, textiles,carpets, leather, wood, paints and plastic articles, cooling lubricantsand other materials which are capable of being attacked or decomposed bymicroorganisms. Other materials to be protected and which can beadversely affected by the multiplication of microorganisms which may bementioned within the scope are parts of production plants and buildings,for example cooling water circuits, cooling and heating systems andaeration and air-conditioning units. Industrial materials which may bementioned by preference within the scope of the present invention areglues, sizes, paper and boards, leather, wood, paints, coolinglubricants and heat-transfer fluids, especially preferably wood. Theactive compounds or compositions according to the invention can preventdisadvantageous effects such as rotting, decay, discoloration,decoloration or mould development. Moreover, the compounds according tothe invention can be employed for protecting objects against beingcovered with growth, in particular ships' hulls, sieves, nets,buildings, jetties and signal units, which come into contact withseawater or brackish water.

The method according to the invention for controlling unwanted fungi canalso be employed for protecting storage goods. Here, storage goods areto be understood as meaning natural substances of vegetable or animalorigin or processed products thereof of natural origin, for whichlong-term protection is desired. Storage goods of vegetable origin, suchas, for example, plants or plant parts, such as stems, leaves, tubers,seeds, fruits, grains, can be protected in the freshly harvested stateor after processing by (pre)drying, moistening, comminuting, grinding,pressing or roasting. Storage goods also include timber, bothunprocessed, such as construction timber, electricity poles andbarriers, or in the form of finished products, such as furniture.Storage goods of animal origin are, for example, pelts, leather, fursand hairs. The active compounds according to the invention can preventdisadvantageous effects, such as rotting, decay, discoloration,decoloration or the development of mould.

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned, by way of example, but not by way oflimitation:

Diseases caused by powdery mildew pathogens, such as, for example,Blumeria species, such as, for example, Blumeria graminis; Podosphaeraspecies, such as, for example, Podosphaera leucotricha; Sphaerothecaspecies, such as, for example, Sphaerotheca fuliginea; Uncinula species,such as, for example, Uncinula necator;Diseases caused by rust disease pathogens, such as, for example,Gymnosporangium species, such as, for example, Gymnosporangium sabinae;Hemileia species, such as, for example, Hemileia vastatrix; Phakopsoraspecies, such as, for example, Phakopsora pachyrhizi and Phakopsorameibomiae; Puccinia species, such as, for example, Puccinia recondita orPuccinia triticina; Uromyces species, such as, for example, Uromycesappendiculatus;Diseases caused by pathogens from the group of the Oomycetes, such as,for example, Bremia species, such as, for example, Bremia lactucae;Peronospora species, such as, for example, Peronospora pisi or P.brassicae; Phytophthora species, such as, for example, Phytophthorainfestans; Plasmopara species, such as, for example, Plasmoparaviticola; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species,such as, for example, Pythium ultimum;Leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, such as, for example, Alternaria solani; Cercosporaspecies, such as, for example, Cercospora beticola; Cladiosporumspecies, such as, for example, Cladiosporum cucumerinum; Cochliobolusspecies, such as, for example, Cochliobolus sativus (conidia form:Drechslera, Syn: Helminthosporium); Colletotrichum species, such as, forexample, Colletotrichum lindemuthanium; Cycloconium species, such as,for example, Cycloconium oleaginum; Diaporthe species, such as, forexample, Diaporthe citri; Elsinoe species, such as, for example, Elsinoefawcettii; Gloeosporium species, such as, for example, Gloeosporiumlaeticolor; Glomerella species, such as, for example, Glomerellacingulata; Guignardia species, such as, for example, Guignardiabidwelli; Leptosphaeria species, such as, for example, Leptosphaeriamaculans; Magnaporthe species, such as, for example, Magnaporthe grisea;Microdochium species, such as, for example, Microdochium nivale;Mycosphaerella species, such as, for example, Mycosphaerella graminicolaand M. fijiensis; Phaeosphaeria species, such as, for example,Phaeosphaeria nodorum; Pyrenophora species, such as, for example,Pyrenophora teres; Ramularia species, such as, for example, Ramulariacollo-cygni; Rhynchosporium species, such as, for example,Rhynchosporium secalis; Septoria species, such as, for example, Septoriaapii; Typhula species, such as, for example, Typhula incarnata; Venturiaspecies, such as, for example, Venturia inaequalis; Root and stemdiseases caused, for example, by Corticium species, such as, forexample, Corticium graminearum; Fusarium species, such as, for example,Fusarium oxysporum; Gaeumannomyces species, such as, for example,Gaeumannomyces graminis; Rhizoctonia species, such as, for example,Rhizoctonia solani; Tapesia species, such as, for example, Tapesiaacuformis; Thielaviopsis species, such as, for example, Thielaviopsisbasicola;Ear and panicle diseases (including maize cobs) caused, for example, byAlternaria species, such as, for example, Alternaria spp.; Aspergillusspecies, such as, for example, Aspergillus flavus; Cladosporium species,such as, for example, Cladosporium cladosporioides; Claviceps species,such as, for example, Claviceps purpurea; Fusarium species, such as, forexample, Fusarium culmorum; Gibberella species, such as, for example,Gibberella zeae; Monographella species, such as, for example,Monographella nivalis; Septoria species, such as, for example, Septorianodorum;Diseases caused by smut fungi, such as, for example, Sphacelothecaspecies, such as, for example, Sphacelotheca reiliana; Tilletia species,such as, for example, Tilletia caries, T. controversa; Urocystisspecies, such as, for example, Urocystis occulta; Ustilago species, suchas, for example, Ustilago nuda, U. nuda tritici;Fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum and P. purpurogenum; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum; Verticilium species, such as, for example,Verticilium alboatrum;Seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Fusarium species, such as, forexample, Fusarium culmorum; Phytophthora species, such as, for example,Phytophthora cactorum; Pythium species, such as, for example, Pythiumultimum; Rhizoctonia species, such as, for example, Rhizoctonia solani;Sclerotium species, such as, for example, Sclerotium rolfsii;Cancerous diseases, galls and witches' broom caused, for example, byNectria species, such as, for example, Nectria galligena;Wilt diseases caused, for example, by Monilinia species, such as, forexample, Monilinia laxa;

Deformations of leaves, flowers and fruits caused, for example, byTaphrina species, such as, for example, Taphrina deformans;

Degenerative diseases of woody plants caused, for example, by Escaspecies, such as, for example, Phaemoniella clamydospora andPhaeoacremonium aleophilum and Fomitiporia mediterranea;Diseases of flowers and seeds caused, for example, by Botrytis species,such as, for example, Botrytis cinerea;Diseases of plant tubers caused, for example, by Rhizoctonia species,such as, for example, Rhizoctonia solani; Helminthosporium species, suchas, for example, Helminthosporium solani;Diseases caused by bacteriopathogens, such as, for example, Xanthomonasspecies, such as, for example, Xanthomonas campestris pv. oryzae;Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans; Erwinial species, such as, for example, Erwinia amylovora.

Preference is given to controlling the following diseases of soya beans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola).

Fungal diseases on roots and the stem base caused, for example, by blackroot rot (Calonectria crotalariae), charcoal rot (Macrophominaphaseolina), fusarium blight or wilt, root rot, and pod and collar rot(Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusariumequiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris),neocosmospora (Neocosmopspora vasinfecta), pod and stem blight(Diaporthe phaseolorum), stem canker (Diaporthe phaseolorum var.caulivora), phytophthora rot (Phytophthora megasperma), brown stem rot(Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythiumirregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum),rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani),sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia Southernblight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsisbasicola).

Organisms which can bring about degradation or modification of theindustrial materials and which may be mentioned are fungi. The activecompounds according to the invention are preferably active againstfungi, in particular moulds, wood-discoloring and wood-destroying fungi(Basidiomycetes). Fungi of the following genera may be mentioned by wayof example: Alternaria, such as Alternaria tenuis; Aspergillus, such asAspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora,such as Coniophora puetana; Lentinus, such as Lentinus tigrinus;Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporusversicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma,such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride.

In addition, the active compounds of the invention also exhibit verygood antimycotic activities. They possess a very broad antimycoticactivity spectrum, in particular against dermatophytes and yeasts,moulds and diphasic fungi (e.g. against Candida species such as Candidaalbicans, Candida glabrata) and also epidermophyton floccosum,Aspergillus species such as Aspergillus niger and Aspergillus fumigatus,Trichophyton species such as Trichophyton mentagrophytes, Microsporonspecies such as Microsporon canis and audouinii. The recitation of thesefungi by no means places any restriction on the mycotic spectrum whichcan be covered, but is only for illustration.

When employing the active compounds according to the invention asfungicides, the application rates may vary within a substantial range,depending on the type of application. The application rate of the activecompounds according to the invention is

-   -   when treating plant parts, for example leaves: from 0.1 to 10        000 g/ha, preferably from 10 to 1000 g/ha, particularly        preferably from 50 to 300 g/ha (when the application is carried        out by watering or dropwise, it may even be possible to reduce        the application rate, in particular when inert substrates such        as rock wool or perlite are used);    -   when treating seed: from 2 to 200 g per 100 kg of seed,        preferably from 3 to 150 g per 100 kg of seed, especially        preferably from 2.5 to 25 g per 100 kg of seed, very especially        preferably from 2.5 to 12.5 g per 100 kg of seed;    -   when treating the soil: from 0.1 to 10 000 g/ha, preferably from        1 to 5000 g/ha.

These application rates are mentioned only by way of example and not byway of limitation in the sense of the invention.

The active compounds or compositions according to the invention can thusbe employed for protecting plants for a certain period of time aftertreatment against attack by the pathogens mentioned. The period forwhich protection is provided extends generally for 1 to 28 days,preferably 1 to 14 days, particularly preferably 1 to 10 days, veryparticularly preferably 1 to 7 days after the treatment of the plantswith the active compounds, or up to 200 days after the treatment ofseed.

In addition, by the treatment according to the invention it is possibleto reduce the mycotoxin content in the harvested material and thefoodstuff and feedstuff prepared therefrom. Particular, but notexclusive, mention may be made here of the following mycotoxins:deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin,fumonisine, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol(DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins,patulin, ergot alkaloids and aflatoxins produced, for example, by thefollowing fungi: Fusarium spec., such as Fusarium acuminatum, F.avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberellazeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F.proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi,F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F.subglutinans, F. tricinctum, F. verticillioides, etc., and also byAspergillus spec., Penicillium spec., Claviceps purpurea, Stachybotrysspec., etc.

The abovementioned plants can be treated especially advantageously inaccordance with the invention with the maleimide salts of the formula(I) or the compositions according to the invention. The preferred rangesindicated above for the active compounds or compositions also apply tothe treatment of these plants. The treatment of plants with thecompounds or compositions mentioned specifically in the present textshould be especially emphasized.

PREPARATION EXAMPLES Example 1

An amount of 10 g (52.9 mmol) of N-methyldichloromaleimide is introducedin 100 ml of absolute methanol. The suspension is admixed dropwise at2-3° C. with 8.455 g (111.1 mmol) of thiourea in solution in 100 ml ofabsolute methanol. Yellow crystals precipitate from the solution at 0-5°C. after about 20 minutes. After a further 10 minutes of subsequentstirring at this temperature, the crystals are filtered off withsuction, the mother liquor is admixed again with 200 ml of cold diethylether, and the subsequently precipitated crystals are likewise filteredoff with suction. Drying gives 13.5 g (74.3% of theory) of[(1-methyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-3,4-diyl)disulphanediyl]bis(aminomethaniminium)dichloride, with a melting point of 163-164° C.

Example 27

An amount of 0.20 g (0.6 mmol) of[(1-methyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-3,4-diyl)disulphanediyl]-bis(aminomethaniminium)dichloride is mixed with 0.12 g (1.2 mmol) of KHCO₃ and the mixture isintroduced with stirring into 2 ml of H₂O/4 ml of ice. Stirring iscontinued until the ice is dissolved, and the brick-red crystals arefiltered off with suction and washed with ice water. Drying gives 50 mg(38.2% of theory) of4-{[amino(iminio)methyl]sulphanyl}-1-methyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-3-thiolate,with a melting point of 150-152° C.

Example 72

An amount of 0.20 g (0.6 mmol) of[(1-methyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-3,4-diyl)disulphanediyl]-bis(aminomethaniminium)dichloride is introduced in 4 ml of water and admixed with 4 ml ofconcentrated ammonia, followed by stirring at 50° C. for 30 minutes, inthe course of which the greenish black suspension turns to reddishblack. It is filtered at room temperature and the filtrate is admixedwith 0.205 g (1.204 mmol) of silver nitrate in 2 ml of H₂O/2 ml ofconcentrated ammonia, and dark brown silver salt precipitates from thedeep-red solution. The precipitate is isolated by filtration withsuction, washed with water/ammonia/methanol and dried. This gives 40 mg(17.1% of theory) of disilver(1+)1-methyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-3,4-bis(thiolate), as an oil.

Example 89

An amount of 1.33 g (4 mmol) of[(1-methyl-2,5-dioxo-2,5-dihydro-1H-pyrrole-3,4-diyl)disulphanediyl]-bis(aminomethaniminium)dichloride is dissolved in water, ammonia is added in excess, the systemis filtered and the filtrate is acidified with 5 ml of concentratedhydrochloric acid. The bright green precipitate is filtered off withsuction and washed with water and a little methanol. Drying gives 0.51 g(72.8% of theory) of 1-methyl-3,4-disulphanyl-1H-pyrrole-2,5-dione, witha melting point of 145-148° C.

In analogy to the examples above and also in accordance with the generaldescriptions of the processes according to the invention, the compoundsof the formula (I) that are given in Table 1 below can be obtained.

TABLE 1 (I)

Ex. Type (2/n X)_(m) R¹ R² R³ R⁴ R⁵ R⁶ R⁷ R⁸ R⁹ M.p. (° C.) 1 (Ia) 2 Cl⁻Me H H H H H H H H 163-164 2 (Ia) 2 Cl⁻ (1S)-1-(4-Chloro- H H H H H H HH 188-192 phenyl)ethyl 3 (Ia) 2 Cl⁻ 1-(4-Chloro- H H H H H H H H 168-195phenyl)ethyl 4 (Ia) 2 Cl⁻ 1-Phenylethyl H H H H H H H H 177-181 5 (Ia) 2Cl⁻ 4-Sulphamoylphenyl H H H H H H H H >250 6 (Ia) 2 Cl⁻ 2-MethoxyethylH H H H H H H H 172-177 7 (Ia) 2 Cl⁻ Bz H H H H H H H H 172-181 8 (Ia) 2Cl⁻ Et H H H H H H H H 167-172 9 (Ia) 2 Cl⁻ 3,5-Dichlorophenyl H H H H HH H H 224-250 10 (Ia) 2 Cl⁻ 3,4-Dichlorophenyl H H H H H H H H 193-19511 (Ia) 2 Cl⁻ 2,4-Dichlorophenyl H H H H H H H H >250 12 (Ia) 2 Cl⁻(Phenylsulphonyl)- H H H H H H H H 155-158 amino 13 (Ia) 2 Cl⁻3-(Trifluoromethyl)- H H H H H H H H 190-195 cyclohexyl 14 (Ia) 2 Cl⁻3-(Trifluoromethyl)- H H H H H H H H 198-205 phenyl 15 (Ia) 2 Cl⁻ ButylH H H H H H H H 161-174 16 (Ia) 2 Cl⁻ Cyclohexyl H H H H H H H H 171-18217 (Ia) 2 Cl⁻ Pr H H H H H H H H 152-164 18 (Ia) 2 Cl⁻ 2-Methylpropyl HH H H H H H H 143-172 19 (Ia) 2 Cl⁻ 2,2-Dimethylpropyl H H H H H H H H172-174 20 (Ia) 2 Cl⁻ iPr H H H H H H H H 162-165 21 (Ia) 2 Cl⁻Cyclopropyl H H H H H H H H 159-164 22 (Ia) 2 Cl⁻ Cyclopropylmethyl H HH H H H H H 160-163 23 (Ia) 2 Cl⁻ H H H H H H H H H 126-153 24 (Ia) 2Cl⁻ Me Me H Me H Me H Me H 135-141 25 (Ia) 2 Cl⁻ Me H H Me Me H H Me Me135-160 26 (Ib) Me Et H Et H 124-260 27 (Ib) Me H H H H 150-152 28 (Ib)Me H H Me H 137-139 29 (Ib) 2-Methoxyethyl H H H H 139-144 30 (Ib) Me HH Et H 125-133 31 (Ib) 3-(Trifluoromethyl)- H H H H 129-131 cyclohexyl32 (Ib) 3,4-Dichlorophenyl H H H H >275 33 (Ib) Me H H Ph H  95-102 34(Ib) Et H H H H 152-154 35 (Ib) Me Prl H Pr H Oil 36 (Ib) Me H H Bz H130-138 37 (lb) H H H H H >210 38 (Ib) Cyclopropylmethyl H H H H 138-13939 (Ib) Pr H H H H 153-158 40 (Ib) Cyclopropyl H H H H 163-168 41 (Ib)Bz H H H H 142-149 42 (Ib) iPr H H H H 155-158 43 (Ib) Cyclohexyl H H HH 142-143 44 (Ib) 3,5-Dichlorophenyl H H H H 182-220 45 (Ib)2,4-Dichlorophenyl H H H H 175-193 46 (Ib) 2-Methylpropyl H H H H141-149 47 (lb) 3-(Trifluoromethyl)- H H H H 170-174 phenyl 48 (Ib) Me HH Me Me 141-143 49 (Ib) Butyl H H H H 149-150 50 (Ib) 1-(4-Chloro- H H HH 155-159 phenyl)ethyl 51 (Ib) (1S)-1-(4-Chloro- H H H H 161-172phenyl)ethyl 52 (Ib) 1-Phenylethyl H H H H 154-157 51 (Ib)(1S)-1-(4-Chloro- H H H H 152-156 phenyl)ethyl 54 (Ib)4-Sulphamoylphenyl H H H H >290 55 (Ib) (Phenylsulphonyl)- H H H H189-193 amino 57 (Ia) 2 Cl⁻ Me H H Me H H H Me H 175-193 58 (Ia) 2 Cl⁻Me H H iPr H H H iPr H 141-148 59 (Ia) 2 Cl⁻ Me H H Ph H H H Ph H113-118 60 (Ia) 2 Cl⁻ Me H H tBu H H H tBu H 121-123 61 (Ia) 2 Cl⁻ Me HH Et H H H Et H 136-141 62 (Ia) 2 Cl⁻ Me H H Bz H H H Bz H 162-166 63(Ia) 2 Cl⁻ Me Me H iPr H Me H iPr H 123-125 64 (Ia) 2 Cl⁻ Me H H Pr H HH Pr H 154-156 65 (Ia) 2 Cl⁻ Me Et H Et H Et H Et H 126-128 66 (Ia) 2Cl⁻ Me Pr H Pr H Pr H Pr H 103-105 67 (Ib) Me H H iPr H 69-72 68 (Ib) MeH H Pr H 145-260 69 (Ib) Me H H tBu H 134-260 70 (Ib) Me Me H iPr H146-260 71 (Ib) 2,2-Dimethylpropyl H H H H 161-164 72 (Ic) 2 Ag⁺ Me Oil73 (Ia) 2 Br⁻ Me H H H H H H H H 116-150 74 (Ic) Zn²⁺ Me >244 75 (Ic) 2Ag⁺ Et Oil 76 (Ia) 2 Br⁻ Me H H Me H H H Me H 148-154 77 (Ia) 2 Br⁻ Me HH Me Me H H Me Me 179-185 78 (Ia) 2 Br⁻ Me H H Et H H H Et H 170-176 79(Ia) 2 Br⁻ Me H H iPr H H H iPr H 173-178 80 (Ia) 2 Br⁻ Me H H Pr H H HPr H 120-122 81 (Ia) 2 Br⁻ Me H H Ph H H H Ph H 107-109 82 (Ia) 2 Br⁻ MeH H Bz H H H Bz H 152-159 83 (Ia) 2 Br⁻ Me H H tBu H H H tBu H 121-12484 (Ia) 2 Br⁻ Me Et H Et H Et H Et H 158-160 85 (Ia) 2 Br⁻ Me Pr H Pr HPr H Pr H 118-120 86 (Ia) 2 Br⁻ Me Me H iPr H Me H iPr H 156-161 87 (Ib)Me Me H Me H 119-130 88 (Ia) 2 Br⁻ Me Me H Me H Me H Me H 153-158 89(Ic) 2 H⁺ Me 145-148 Me = methyl, Et = ethyl, Pr = n-propyl, iPr =propan-2-yl tBu = tert-butyl, Ph = phenyl, Bz = benzyl For the sake ofsimplicity, there is an indication in each case of the subgroup to whichthe compound in question belongs, namely the compunds of the formulae(Ia), (Ib) or (Ic).

Use Examples Example A Phytophthora Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

An appropriate preparation of active compound is produced by mixing onepart by weight of active compound with the stated amounts of solvent andemulsifier and diluting the concentrate with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are inoculated with anaqueous spore suspension of Phytophthora infestans. The plants are thenplaced in an incubation cabin at about 20° C. and 100% relativehumidity. Evaluation takes place 3 days after inoculation. Here, 0%denotes an efficacy which corresponds to that of the control, whereas anefficacy of 100% means that no infestation is observed. In this test,the compounds 1, 6, 8, 10, 17, 18, 22, 23, 26, 27, 28, 32 and 37according to the invention, at an active compound concentration of 250ppm, exhibit an efficacy of 70% or more.

Example B Venturia Test (Apple)Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

An appropriate preparation of active compound is produced by mixing onepart by weight of active compound with the stated amounts of solvent andemulsifier and diluting the concentrate with water to the desiredconcentration. To test for protective activity, young plants are sprayedwith the preparation of active compound at the stated application rate.After the spray coating has dried on, the plants are inoculated with anaqueous conidia suspension of the apple scab pathogen Venturiainaequalis, and then spend 1 day in an incubation cabin at about 20° C.and 100% relative humidity. The plants are then placed in a greenhouseat about 21° C. under a relative humidity of around 90%. Evaluationtakes place 10 days after inoculation. Here, 0% denotes an efficacywhich corresponds to that of the control, whereas an efficacy of 100%means that no infestation is observed. In this test, the compounds 1, 6,8, 10, 17, 22, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42 and 44 according to the invention, at an active compoundconcentration of 250 ppm, exhibit an efficacy of 70% or more.

1. A method of controlling phytopathogenic fungi, comprising applying acomposition containing at least one compound of formula (I)

in which (a) Y¹ is the group of the formula (II)

Y² is the group of the formula (III)

m is 1, n is the ionic charge of X, and X is an anion selected from Cl⁻or Br⁻, (b) Y¹ is the group of the formula (II)

Y² is —S⁻, and m is 0, or (c) Y¹ is —S⁻, Y² is —S⁻, m is 1, n is theionic charge of X, and X is a cation selected from H⁺, Ag⁺, Co²⁺, Cu²⁺,Fe²⁺, Mn²⁺, Ni²⁺, Pd²⁺, Zn²⁺, and R¹ is hydrogen; C₁-C₈-alkyl optionallysubstituted with one or more identical or different halogen, —OR¹⁰, or—COR¹¹; C₃-C₇-cycloalkyl or C₃-C₇-cyclo-alkyl-C₁-C₂-alkyl, each of whichis optionally substituted with one or more identical or differenthalogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl; or aryl, aryl-(C₁-C₄-alkyl),or arylsulphonylamino, each of which is optionally substituted in thearyl moiety with one or more identical or different halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR¹¹, or sulphonylamino, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, and R⁹ independently of one another are hydrogen,C₁-C₆-alkyl, or phenyl or benzyl, each of which is optionallysubstituted with one or more identical or different halogen,C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio, R¹⁰ is hydrogen,C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which is optionallysubstituted with one or more halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,and R¹¹ is hydroxyl, C₁-C₄-alkyl, or C₁-C₄-alkoxy to the fungi, theirhabitat, or a combination thereof.
 2. The method of claim 1, wherein R¹is hydrogen; C₁-C₆-alkyl optionally substituted with one or moreidentical or different fluorine, chlorine, bromine, —OR¹⁰, or —COR¹¹;C₃-C₇-cycloalkyl or C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which isoptionally substituted with one or more identical or different chlorine,methyl, or trifluoromethyl; or phenyl, phenyl-(C₁-C₄-alkyl), orphenylsulphonylamino, each of which is optionally substituted with oneor more identical or different fluorine, chlorine, bromine, methyl,trifluoromethyl, —COR¹¹, or sulphonylamino, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,and R⁹ independently of one another are hydrogen, C₁-C₄-alkyl, phenyl,or benzyl, R¹⁰ is hydrogen, methyl, ethyl, methylcarbonyl, orethylcarbonyl, or phenyl which is optionally substituted with one ormore fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, ortrifluoromethyl, and R¹¹ is hydroxyl, methyl, ethyl, methoxy, or ethoxy;with the proviso that if X is an anion, then X is Cl⁻; and if X is acation, then X is H⁺, Ag⁺, Fe²⁺, Mn²⁺, or Zn²⁺.
 3. The method of claim1, wherein R¹ is hydrogen; C₁-C₅-alkyl optionally substituted with oneor more identical or different fluorine, chlorine, hydroxyl, methoxy,ethoxy, methylcarbonyloxy, or carboxyl; cyclopropylmethyl orC₃-C₇-cycloalkyl optionally substituted with one or more identical ordifferent chlorine, methyl, or trifluoromethyl; or phenyl, benzyl,1-phenethyl, 2-phenethyl, or 2-methyl-2-phenethyl, each of which isoptionally substituted with one to three identical or differentfluorine, chlorine, bromine, methyl, trifluoromethyl, —COR¹¹, orsulphonylamino, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ independently of oneanother are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, sec-butyl, or tert-butyl, R¹⁰ is hydrogen, methyl,methylcarbonyl, or phenyl, and R¹¹ is hydroxyl or methoxy; with theproviso that if X is an anion, then X is Cl⁻; if X is a cation, then Xis Ag⁺, Mn²⁺, or Zn²⁺.
 4. The method of claim 1, further comprising oneor more extenders, surface-active substances, or a combination thereof.5. (canceled)
 6. A compound of formula (IV)

in which R^(1a) is hydrogen; C₁-C₈-alkyl optionally substituted with oneor more identical or different halogen, —OR^(10a), or —COR^(11a);C₃-C₇-cycloalkyl or C₃-C₇-cyclo-alkyl-C₁-C₂-alkyl, each of which isoptionally substituted with one or more identical or different halogen,C₁-C₄-allyl, or C₁-C₄-haloalkyl; or aryl, aryl-(C₁-C₄-alkyl), orarylsulphonylamino, each of which is optionally substituted in the arylmoiety with one or more identical or different halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, —COR^(11a), or sulphonylamino, R^(2a), R^(3a), R^(4a),R^(5a), R^(6a), R^(7a), R^(8a), and R^(9a) independently of one anotherare hydrogen, C₁-C₆-alkyl, or phenyl or benzyl, each of which isoptionally substituted with one or more identical or different halogen,C₁-C₄-alkyl, C₁-C₄-alkoxy, or C₁-C₄-alkylthio, R^(10a) is hydrogen,C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which is optionallysubstituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkylsubstituents, R^(11a) is hydroxyl, C₁-C₄-alkyl, or C₁-C₄-alkoxy, m is 1,n is the ionic charge of X^(a), and X^(a) is an anion selected from Cl⁻or Br⁻; with the proviso that if R^(1a) is hydrogen, methyl,hydroxymethyl, methylcarbonyloxymethyl, chloromethyl, benzyl, phenyl, ormethoxymethyl and X^(a) is Cl⁻, then R^(2a), R^(3a), R^(4a), and R^(5a)are not all simultaneously hydrogen.
 7. A compound of formula (V)

in which R^(1b) is hydrogen; C₁-C₈-alkyl optionally substituted with oneor more identical or different halogen, —OR^(10b), or —COR^(11b);C₃-C₇-cycloalkyl or C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which isoptionally substituted with one or more identical or different halogen,C₁-C₄-alkyl, or C₁-C₄-haloalkyl; or aryl, aryl-(C₁-C₄-alkyl), orarylsulphonylamino, each of which is optionally substituted in the arylmoiety with one or more identical or different halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, —COR^(11b), or sulphonylamino, R^(2b), R^(3b), R^(4b),and R^(5b), independently of one another are hydrogen, C₁-C₆-alkyl, orphenyl or benzyl, each of which is optionally substituted with one ormore identical or different halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, orC₁-C₄-allylthio, R^(10b) is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl,or aryl which is optionally substituted with one or more halogen,C₁-C₄-alkyl, or C₁-C₄-haloalkyl, and R^(11b) is hydroxyl, C₁-C₄-alkyl,or C₁-C₄-alkoxy, with the proviso that if R^(1b) is hydrogen, methyl,hydroxymethyl, methylcarbonyloxymethyl, chloromethyl, benzyl, phenyl, ormethoxymethyl, then R^(2b), R^(3b), R^(4b), and R^(5b) are not allsimultaneously hydrogen.
 8. A compound of formula (VI)

in which R^(1c) is hydrogen; C₁-C₈-allyl optionally substituted with oneor more identical or different halogen, —OR^(10c), or —COR^(11c);C₃-C₇-cycloalkyl or C₃-C₇-cycloalkyl-C₁-C₂-alkyl, each of which isoptionally substituted with one or more identical or different halogen,C₁-C₄-alkyl, or C₁-C₄-haloalkyl; or aryl, aryl-(C₁-C₄-alkyl), orarylsulphonylamino, each of which is optionally substituted in the arylmoiety with one or more identical or different halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, —COR^(11c), or sulphonylamino, R^(10c) is hydrogen,C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or aryl which is optionallysubstituted with one or more halogen, C₁-C₄-alkyl, or C₁-C₄-haloalkyl,R^(11c) is hydroxyl, C₁-C₄-alkyl, or C₁-C₄-alkoxy, m is 1, n is theionic charge of X^(c), and X^(c) is a cation selected from Ag⁺, Co²⁺,Cu²⁺, Fe²⁺, Mn²⁺, Ni²⁺, Pd²⁺, Zn²⁺, with the proviso that if R^(1c) ishydrogen, methyl, hydroxymethyl, methylcarbonyloxymethyl, chloromethyl,benzyl, phenyl, or methoxymethyl, then X^(c) is not Ag⁺.